DE19732030B4 - Process for the preparation of chloromethanesulfonyl chloride - Google Patents

Abstract

Process for the preparation of chloromethanesulfonyl chloride of the formula ClCH ₂ SO ₂ Cl, characterized in that the sodium salt of the chloromethanesulfonic acid of the formula ClCH ₂ SO ₂ ONa, which is used in the form of a dried crude product of the known reaction of dichloromethane with sodium sulfite, suspended in phosphoryl chloride as a solvent and reacted with a chlorinating agent.

Description

The The present invention relates to a novel process for the preparation of chloromethanesulfonyl chloride, compared to the previously described methods has considerable advantages for the preparation of this compound.

The compound to be prepared by the process according to the invention chloromethanesulfonyl chloride is a known compound. It has the formula ClCH ₂ SO ₂ Hal where Hal is chlorine.

Of the Chemical literature is used to prepare chloromethanesulfonyl chloride to take different methods, the following three basic types of procedures can be assigned:

In the German patent DE 836492 describes the preparation of chloromethanesulfonyl chloride by reacting paraformaldehyde, concentrated aqueous hydrochloric acid, hydrogen sulfide and chlorine.

At the second type of process, e.g. is described in Brintzinger et al., Chemische Berichte 85, 1952, pp. 455/456; Douglass, Simpson, Sawyer, J. Org. Chem. 14, 1949, p. 273; Douglass, Simpson, Sawyer, J. Org. 5, 1940, p. 84, Symmetrical Trithian Among Varied Conditions chlorinated. In this process falls next to the desired Chloromethanesulfonyl chloride on a series of by-products.

According to one The third type of process involves the preparation of chloromethanesulfonyl chloride from dimethyl disulfide or chloromethyl sulfur chloride and chlorine (Douglass, Simpson, Sawyer, J. Org. Chem. 14, 1949, p. 273). Also this procedure leads to a big one Amount of by-products.

All The types of process described are based on oxygen-free sulfur compounds (hydrogen sulphide, Trithiane, dimethyldisulfide or chloromethylsulfur chloride), the as such are unpleasant to handle and from which also by-products arise that the process implementation with a considerable Burden the expense.

Attempts to circumvent these disadvantages, for example, by trying to produce chloromethanesulfonyl chloride by similar methods as the homologous β-chloroethanesulfonyl chloride, which is commercially available and, for example, starting material for that in the German patent DE 195 15 976 described process for Taurinamidherstellung is failed. The process of radically chlorinating ethanesulfonic acid which is carried out in the art for the preparation of β-chloroethanesulfonyl chloride does not give any useful results since di- and trihalogenated compounds are formed.

In the introduction to the German patent DE 836 492 The paragraph has also been found: "Chlorinated sulfochlorides containing the chlorine and the sulfochloride group on the same aliphatically bonded carbon atom have hitherto been prepared from the corresponding sulfonic acids by treatment with suitable chlorides, eg PCl _5. This process is of course cumbersome and costly . " It is not apparent from the said paragraph, which chlorinated sulfochlorides should have been prepared according to the outlined process and which sulfonic acids were reacted in which form and under which conditions with chlorinating agents. In any case, it is not possible to deduce from the literature which has become known a process for the preparation of chloromethanesulfonyl chloride which corresponds to the outlined process concept. The reference to the inconvenience and expense of methods of the type mentioned prevents the skilled person to expect a simple, cheap solution to the problem of producing chloromethanesulfonyl chloride from processes of the type mentioned, in particular also with regard to the following in the German patent DE 836 492 as a "simple" procedure described, in which one works with the gaseous, toxic and aggressive hydrogen sulfide and chlorine and the. requires a time of the order of 9 to 12 hours and varying reaction temperatures between 60 ° C and -15 ° C until completion of the chemical reactions.

It There is therefore a need for a new, simple, clean and with high yield feasible Process for the preparation of chloromethanesulfonyl chloride, which, similar to that in large quantities manufactured and used in the pharmaceutical and agrochemical industries Chloroacetyl chloride consumed as a building block, a promising key building block for the Synthesis of drugs and crop protection agents, for example for the preparation of various chloromethylsulfonamide derivatives with pharmaceutical effect or other biological activity.

These The object is achieved by a method according to claim 1.

A Preferred embodiment of the method according to the invention is claimed 2 reproduced.

The process according to the invention is based essentially on the fact that the starting point for the preparation of chloromethanesulfonyl chloride is a starting compound which has not yet been used for this purpose, namely the nartium salt of chlorme thansulfonsäure.

The selected as the starting compound Nartium salt of chloromethanesulfonic acid is not available commercially, However, according to the chemical literature removable method easy to produce and in good yield. A particularly advantageous method based on the reaction of dichloromethane (methylene chloride) with an alkali metal sulfite, e.g. Sodium sulfite, and is described, for example in German Patent 414426. Another known method is in the reaction of aminomethanesulfonic acid with sodium nitrite and concentrated hydrochloric acid (Backer, Mulder, R. 52 (1933), p. 456).

A Post-processing of starting from methylene chloride and sodium sulfite Method by the inventors provided a crude product, which in a Reaction rate between 70 and 100 chloromethanesulfonic acid in salt form, Sodium sulfite and sodium chloride. This crude product can directly as a dry powder according to the invention with phosphorus pentachloride in Phosphoryl chloride (phosphorus oxychloride) to the desired Chlormethansulfonylchlorid be chlorinated.

in the Contrary to the corresponding hydroxymethanesulfonic proved the chloromethanesulfonic acid under chlorinating conditions as stable and can in per se known Be chlorinated using known chlorinating agents. The chlorinating agents are in particular those chlorinating agents in a generalized consideration as acid chlorides inorganic acids can be viewed and to which phosphoryl chloride, thionyl chloride or phosgene and the more aggressive chlorinating agents such as phosphorus trichloride and phosphorus pentachloride belong.

Puts Chloromethanesulfonic acid in the form of the chloromethanesulfonic acid sodium salt, with chlorinating agents of the type mentioned in the solvent Phosphoryl chloride to, so receives the known compound chloromethanesulfonyl chloride in good Yield and purity.

A Reaction of hydroxymethanesulfonic acid sodium salt leads to decomposition.

Is working with phosphorus pentachloride as the chlorinating agent and in phosphoryl chloride as a solvent, Thus, a quantitative implementation of the sodium salt of chloromethane sulfonic acid is achieved. at Room temperature, the reaction is completed after 30 min. by virtue of The simplicity and cleanliness of the above implementation proved Phosphoryl chloride as an for the inventive method particularly suitable for the preparation of chloromethanesulfonyl chloride Solvent.

following The invention will be explained in more detail with reference to an embodiment.

example

1. Preparation of the sodium salt of chloromethanesulfonic acid

In analogous reworking of the German patent DE 414426 575 g of sodium sulfite were dissolved in 2300 ml of water and added together with 598 ml of dichloromethane and 138 ml of ethanol as a solubilizer in a pressure vessel, which was sealed and overnight in an oil bath at a temperature of 120 ° C was held.

To 12 hours became the entire liquid from the pressure vessel in a vacuum away. The solid residue was to remove any residual water with a little isopropanol offset and azeotropically dried by its removal by vacuum. The obtained solid dry powder was without further purification further processed.

2. Production of chloromethanesulfonyl chloride

In a suitable reaction vessel (flask with a mechanical stirrer), the sodium salt of chloromethanesulfonic acid prepared above according to 1 was suspended as a crude product without further purification in phosphoryl chloride. The mixture was treated with such an amount of phosphorus pentachloride, which corresponded to a stoichiometric reaction of the sodium salt of the chloromethanesulfonic acid to form Chlormethansulfonylchlorid and simultaneous formation of phosphoryl chloride from phosphorus pentachloride. The reaction mixture was stirred at room temperature until the reaction was complete (about 30 minutes). Subsequently, the phosphoryl chloride was distilled off, and the residue was added with ice water. The organic phase was diluted to a higher volume by the addition of dichloromethane and separated from the aqueous phase. After drying the organic phase by addition of a drying agent (sodium sulfate) and separation of the drying agent, the solvent is first removed by distillation and then the product Chlormethansulfonylchlorid obtained by distillation. The Chlormethansulfonylchlorid is obtained as a water-clear liquid with a boiling point Kp ₁₂ 63 ° C (according to the prepublished literature).

outgoing of one mole (152 g) of sodium chloride of the chloromethanesulfonic acid gives the product Chloromethanesulfonyl chloride in 90% yield.

The product has the following nuclear resonance spectra, which can not yet be deduced from the known literature (in CDCl ₃ ):
1 H NMR (CDCl ₃ , 200 MHz): δ (ppm) = 5.00 (s, 2H)
13 C-NMR (CDCl ₃ , 50.3 MHz): δ (ppm) = 65.57 (CH ₂ )

Claims (2)

Process for the preparation of chloromethanesulfonyl chloride of the formula ClCH ₂ SO ₂ Cl, characterized in that the sodium salt of the chloromethanesulfonic acid of the formula ClCH ₂ SO ₂ ONa, which is used in the form of a dried crude product of known per se conversion of dichloromethane with sodium sulfite, suspended in phosphoryl chloride as a solvent and reacted with a chlorinating agent. Method according to claim 1, characterized in that that as the chlorinating agent phosphorus pentachloride in stoichiometric Add quantities.